EP1969024A1 - Verfahren zur herstellung von oxymethylen-polymeren, ausgewählte polymere und deren verwendung - Google Patents
Verfahren zur herstellung von oxymethylen-polymeren, ausgewählte polymere und deren verwendungInfo
- Publication number
- EP1969024A1 EP1969024A1 EP06840978A EP06840978A EP1969024A1 EP 1969024 A1 EP1969024 A1 EP 1969024A1 EP 06840978 A EP06840978 A EP 06840978A EP 06840978 A EP06840978 A EP 06840978A EP 1969024 A1 EP1969024 A1 EP 1969024A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxymethylene
- polymer
- reaction mixture
- polymerization
- trioxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 57
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000178 monomer Substances 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 229920001519 homopolymer Polymers 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 21
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011541 reaction mixture Substances 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 26
- 230000009849 deactivation Effects 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 13
- 150000001241 acetals Chemical class 0.000 claims description 12
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 7
- 239000006085 branching agent Substances 0.000 claims description 6
- 238000012674 dispersion polymerization Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 150000005215 alkyl ethers Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 125000006353 oxyethylene group Chemical group 0.000 claims description 2
- CZLMRJZAHXYRIX-UHFFFAOYSA-N 1,3-dioxepane Chemical compound C1CCOCOC1 CZLMRJZAHXYRIX-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 239000008240 homogeneous mixture Substances 0.000 claims 1
- 125000000962 organic group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 13
- 229920006324 polyoxymethylene Polymers 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- -1 polyoxymethylenes Polymers 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FZIIBDOXPQOKBP-UHFFFAOYSA-N 2-methyloxetane Chemical compound CC1CCO1 FZIIBDOXPQOKBP-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- YBGKQGSCGDNZIB-UHFFFAOYSA-N arsenic pentafluoride Chemical compound F[As](F)(F)(F)F YBGKQGSCGDNZIB-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- STENYDAIMALDKF-UHFFFAOYSA-N cyclobutane-1,3-diol Chemical compound OC1CC(O)C1 STENYDAIMALDKF-UHFFFAOYSA-N 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical class OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- NGCMLEQSKQCTAK-UHFFFAOYSA-N tetraoxane Chemical compound C1COOOO1 NGCMLEQSKQCTAK-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/10—Polymerisation of cyclic oligomers of formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/30—Chemical modification by after-treatment
- C08G2/34—Chemical modification by after-treatment by etherification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/30—Chemical modification by after-treatment
- C08G2/36—Chemical modification by after-treatment by depolymerisation
Definitions
- the present invention relates to an improved process for the preparation of oxymethylene homo- and copolymers as well as selected oxymethylene homo- and copolymers and their use.
- the preparation of polyoxymethylenes is known per se.
- the polymerization can be carried out both in bulk and in solution as a precipitation polymerization and without pressure or under pressure.
- Chain transfer agents for example methylal, have also been used for the preparation of oxymethylene polymers.
- cationic initiators are used.
- a disadvantage of the use of cationic initiators is that they also catalyze the reverse reaction, ie the degradation of the POM in formaldehyde. After the polymerization, therefore, the reaction mixture must be deactivated.
- Deactivation in the polymer melt limits the viscosity of the speed of mixing in the deactivator. Although the viscosity can be increased by increasing the temperature, this also favors the speed of the Polymer degradation. Upon deactivation with protic compounds, chain scission occurs at elevated temperatures, for example by hydrogen transfer reaction.
- J P-A-04 / 114,003 and JP-A-04 / 145,114 describe the deactivation of the polymerization catalyst in oxymethylene homo- or copolymer mixtures by adding mixtures of selected oxides and melting the mixture.
- ester terminated capped oxymethylene polymers degrade at elevated temperatures or in basic or acidic environments, are characterized by ether-end capped oxymethylene polymers by a very high stability.
- the previously proposed methods for the preparation of these polymers always included a separate step for the capping of the polymers. Although this separate reaction leads to a significantly increased stability of the polymers; However, further improvements are desirable because the formaldehyde emission during further processing and application should be kept as low as possible and excluded as far as possible.
- the object of the present invention is to provide a simple process for the preparation of oxymethylene homo- or copolymers (hereinafter also referred to as "POM”) of high stability, which allows an efficient deactivation of the reaction mixture.
- POM oxymethylene homo- or copolymers
- Another object of the present invention is to provide a process for producing POM of high stability, which is to be carried out with simple means and energetically favorable.
- Yet another object of the present invention is to provide selected oxymethylene homopolymers and copolymers characterized by very high stability.
- the present invention relates to a process for the preparation of oxymethylene
- Initiator of the cationic polymerization and ii) deactivation of the initiator and / or the active polymer chains by treatment of the polymer produced in step i) in homogeneous phase with an aprotic solvent which is basic and / or which contains a dissolved base.
- the invention relates to a process for the preparation of oxymethylene copolymers comprising the structural units of the formulas II and III and end groups of the formula IV
- R 1 is an alkyl group
- m is an integer of 1 to 1000
- o is an integer of 2 to 6
- p is an integer of 3 to 6
- R 3 is a p-valent organic radical comprising the steps of: i) heterogeneous polymerization of a -CH 2 -O- units forming
- Phase with an aprotic solvent which is basic and / or which contains a dissolved base.
- R 1 and R 2 independently of one another are alkyl radicals, in particular C 1 to C 6 alkyl radicals, which are preferably straight-chain. Most preferably, R 1 and R 2 are independently methyl, ethyl, propyl or butyl.
- R 3 is derived from a branch.
- branching agents for example, trihydric or higher alcohols or their derivatives, preferably trihydric to hexahydric alcohols or derivatives thereof are used. Preferred derivatives are
- R 3 can thus be a p-valent organic radical, preferably a p-valent alkyl radical, for example a trivalent radical of the formula -CH 2 -CH (R '-) -, where R ' is alkylene, such as methylene or ethylene ,
- n is preferably 500 to 10,000, especially 500 to 3,000.
- Index m is preferably 1 to 300.
- Index o is preferably 2 to 4, especially 2.
- Index p is preferably 3 to 4.
- Step i) of the process according to the invention is a known polymerization of monomers which form -CH 2 -O- units and optionally further comonomers and / or branching agents.
- the polymerization is carried out heterogeneously, ie in the presence of liquid and solid phase, preferably as a precipitation polymerization.
- a -CH 2 -O- units forming monomer or a mixture of different monomers with conventional initiators of cationic polymerization and with acetals of formaldehyde as a regulator in a conventional manner.
- the polymerization can be carried out without pressure or preferably at pressures up to
- 500 bar for example, at pressures between 2 and 500 bar done.
- the polymerization temperature is below the melt temperature of the resulting homo- or copolymers.
- Typical polymerization temperatures for precipitation are in the range of 60 to 140 ° C, preferably from 70 to 120 0 C.
- Preferred pressures for the precipitation are in the range from 0 to 10 bar.
- the oxymethylene homopolymers or copolymers are generally unbranched linear polymers which are generally at least 50 mol%, preferably at least 80 mol%, in particular at least 90 mol%, of oxymethylene units (-CH 2 -O -) contain. If desired, small amounts of branching agents can be used. Usually, the amount of branching agent is not more than 1 wt .-%, based on the total amount of monomers used to prepare the oxymethylene homopolymers or copolymers, preferably not more than 0.3 wt .-%.
- the molecular weights, characterized as volume melt index MVR, of these polymers can vary within wide ranges. Typical MVR values are 0.1 to 100 ml / 10 min, preferably 1 to 80 ml / 10 min, measured according to EN
- Oxymethylene homopolymers are derived from formaldehyde or its cyclic ones Oligomers, such as trioxane or tetroxane, from.
- Oxymethylene copolymers are derived from formaldehyde or its cyclic oligomers, in particular from trioxane, and from cyclic ethers, aldehydes, such as glyoxylic acid esters, cyclic acetals, which may optionally be substituted, and / or linear oligo- or polyacetals.
- Trioxocane as cyclic ethers and linear oligo- or polyformals, such as
- Polydioxolane or polydioxepane called co-components.
- Oxymethylene homopolymers are preferably prepared in which at least 90%, preferably at least 95% and most preferably at least 98% of all end groups alkyl ether groups, especially methoxy or
- Ethoxy groups are. Very particularly preferably produced oxymethylene homopolymers are derived from trioxane.
- Preferred copolymers contain 99.9-85 mol% of structural units of the formula - (CH 2 -O-) m , preferably derived from trioxane, and 0.1 to 15 mol% of repeating structural units derived from one of the abovementioned comonomers, in particular CH 2 -CH 2 -O- units.
- Polymers having repeating structural units which can be prepared, for example, by reacting trioxane, one of the cyclic ethers described above, and with a third monomer, preferably a bifunctional compound of the formula, can also be prepared as oxymethylene copolymers
- Preferred monomers of this type are ethylene diglycidyl, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in the molar ratio 2: 1, and diether from 2 mol glycidyl compound and 1 mol of an aliphatic diol having 2 to 8 carbon atoms, such as the diglycidyl ethers of ethylene glycol , 1, 4-butanediol,
- a trifunctional compound such as trimethylolpropane triglycidyl ether can be used as the third monomer.
- Particularly preferably used -CH 2 -O units forming monomers are formaldehyde or very particularly preferably trioxane.
- the resulting polymer precipitates from the initial liquid polymerization mixture.
- the molecular weight of the resulting (co) polymers is adjusted by using acetals of formaldehyde (chain transfer agent). These also lead to the formation of alkyl ether end groups of the (co) polymer, leaving a separate
- the chain transfer agents used are monomeric or oligomeric acetals of formaldehyde.
- Preferred chain transfer agents are compounds of the formula VI
- R 1 and R 2 independently of one another are alkyl radicals, such as butyl, propyl, ethyl and in particular methyl, and q is an integer from 1 to 100.
- the chain transfer agents are usually used in amounts of up to 50,000 ppm, preferably from 100 to 5,000 ppm, particularly preferably 500 to 1,500 ppm, based on the monomer (mixture).
- Suitable initiators are the cationic initiators customarily used in the preparation of oxymethylene homopolymers or copolymers.
- Examples are protic acids, such as fluorinated or chlorinated alkyl and
- Arylsulfonic acids e.g. Trifluoromethanesulfonic acid, trifluoromethanesulfonic anhydride, or Lewis acids, e.g. Tin tetrachloride, arsenic pentafluoride, phosphorus pentafluoride and boron trifluoride, and their complex compounds, such as e.g. Boron trifluoride etherates, and carbocation sources, such as triphenyl methyl hexafluorophosphate.
- Lewis acids e.g. Tin tetrachloride, arsenic pentafluoride, phosphorus pentafluoride and boron trifluoride
- Lewis acids e.g. Tin tetrachloride, arsenic pentafluoride, phosphorus pentafluoride and boron trifluoride
- complex compounds such as e.g. Boron trifluoride etherates, and carbocation sources, such as triphen
- the initiators are usually used in amounts of from 0.005 to 50 ppm, preferably from 0.01 to 5 ppm, more preferably from 0.02 to 2 ppm, based on the monomer (mixture).
- the solid or liquid polymerization mixture is treated with an aprotic solvent which is basic and / or contains a dissolved base in homogeneous phase.
- an aprotic solvent which is basic and / or contains a dissolved base in homogeneous phase.
- bases such compounds are used, which lead to the termination of the polymerization.
- bases include proton acceptors such as triethylamine and basic aprotic solvents such as dimethylformamide. It is therefore possible to use basic aprotic solvents alone as deactivators or aprotic solvents, which need not necessarily be basic, in combination with a base dissolved therein.
- An example of this is a solution of triethylamine in dimethyl sulfoxide or a solution of triethylamine in Trioxane.
- the treatment with the deactivator solution of aprotic solvent and optionally a base can be carried out by isolating the resulting polymer and rapidly dissolving in the deactivator solution. Deactivation of the
- Polymers can be made by isolation of the oxymethylene homo- or copolymers prepared in step i) after polymerization, for example by cooling the polymer melt and grinding to powder followed by dissolving this powder in the aprotic solvent which is basic and / or contains a dissolved base ,
- the hot precipitation polymer can be introduced into the aprotic solvent, which is basic and / or contains a dissolved base.
- the polymers precipitated during the polymerization are melted by increasing the temperature and the resulting homogeneous phase is treated with the deactivator solution.
- the deactivation of the polymer by direct treatment of the produced in step i) oxymethylene homo- or copolymer is carried out after the polymerization by the hot precipitation polymer is melted by heating and with the aprotic solvent which is basic and / or a dissolved Base contains, is treated.
- the inventive method preferably comprises between steps i) and ii) a step ia), wherein the reaction mixture, optionally together with an aprotic solvent for the polymer is heated, so that a homogeneous
- the heating may be accomplished by heating the deactivator vessel and / or by supplying a hot deactivator solution.
- the proportion of solvent must be selected sufficiently to be able to achieve a homogeneous phase at the temperatures and pressures of the deactivation step. Typically, at least 10% by weight, preferably 20 to 80% by weight of solvent, based on the weight of polymer, is required. Typical deactivation temperatures range from 120 ° C. to 200 ° C., preferably from 130 ° C. to 160 ° C.
- Typical deactivation pressures range from 1 to 500 bar, preferably from 1 to 50 bar.
- solvents for the deactivation step are polar and aprotic solvents, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, or cyclic acetals, dioxolane and especially trioxane.
- the solvent may itself be basic or contains a dissolved base, preferably primary, secondary or especially tertiary amines.
- an aprotic organic solvent in particular trioxane, which contains an amine, preferably a tertiary amine, very particularly preferably triethylamine or a primary amine, preferably melamine.
- Polymerization and deactivation can take place in the reactors known for the preparation of homo- or POM copolymers.
- steps i) and ii) are carried out at elevated temperatures and pressures.
- steps i) and ii) are carried out two reactors connected in series.
- the polymerization time can vary widely and typically ranges from 10 seconds to 2 hours, preferably from 15 seconds to 1 hour, and more preferably from 20 to 50 seconds.
- the actual deactivation takes place instantaneously and ends with the homogeneous mixing of the components.
- the time required for homogenization is in the range of typically 5 seconds to 5 minutes.
- Copolymers can be stabilized by targeted degradation of the polymer chains produced up to a stabilizing monomer unit. These measures are known per se.
- Particularly preferred is a process in which no additional measures for chain closure, such as esterification or etherification of the chain ends, more are made.
- Relaxation zone are transferred and by applying a reduced pressure residual monomers and solvents are removed.
- the removal can also take place in several stages, wherein the first stages can also be operated above atmospheric pressure.
- the relaxation zone is formed by a space that is filled by the hot polymer solution.
- a negative pressure preferably a pressure of less than 500 mbar, in particular less than 200 mbar, the majority of the remaining monomer and solvent residues is expelled by utilizing the temperature of the polymer solution from this.
- Process step can be carried out in a separated part of the tubular reactor, preferably in an extruder. But it can also be used other aggregates, such as a flash chamber.
- pressurized Polymer solutions are first reduced to ambient pressure in the expansion zone before the residual monomers are exhausted.
- the polymer solution is transferred to step ii) while maintaining the pressure in an extruder, in which the relaxation and the
- twin-screw extruder is used.
- the relaxation zone may optionally already stabilizers and
- additives should be selected such that they are not removed from the polymer by the subsequent extraction step.
- the mixture of additives may contain processing aids, for example adhesion promoters, lubricants, nucleating agents, mold release agents, fillers, reinforcing materials or antistatic agents and additives which impart a desired property to the molding composition, such as dyes and / or pigments and / or impact modifiers and / or electrical conductivity imparting agents Additions; and mixtures of these additives, but without limiting the scope of the examples mentioned.
- processing aids for example adhesion promoters, lubricants, nucleating agents, mold release agents, fillers, reinforcing materials or antistatic agents and additives which impart a desired property to the molding composition, such as dyes and / or pigments and / or impact modifiers and / or electrical conductivity imparting agents Additions; and mixtures of these additives, but without limiting the scope of the examples mentioned.
- Granulation and extraction can be done in known aggregates.
- Drying is preferably followed by the extraction stage in order to remove the granules from residues of the adhering extractant.
- the polymer may optionally be provided with additives in a manner known per se.
- additives in this process stage, it is also possible to add those additives which would have been dissolved out of the polymer in the extraction stage.
- the first reactor (1) In the first reactor (1) is introduced a mixture of -CH 2 -O group-forming monomer, preferably trioxane, together with an acetal of formaldehyde (4), preferably methylal, and an initiator of cationic polymerization (5).
- the precipitation polymerization for example at temperatures of 80 0 C and pressures of 1 to 10 bar.
- the average residence time of the reaction mixture in the first reactor is about 30 seconds.
- An amine (6) optionally dissolved in trioxane, is added to the reaction mixture.
- the trioxane content in the second reactor (2) is adjusted so that it is at least 10 wt .-%, based on the polymer.
- the reaction mixture is heated, for example to temperatures of 150 0 C.
- the average residence time of the reaction mixture in the second reactor is also about 30 seconds.
- a solution of the polymer in trioxane forms.
- the reaction mixture is transported to the third reactor (3).
- Trioxane, monomer residues and optionally further volatile constituents (7) are removed from the reaction mixture here. This takes place in the illustrated
- Embodiment in several stages.
- an unrepresented additization of the POM can be carried out with the additives described above.
- the end product is discharged from the reactor as stream (8).
- FIG. 1 describes a preferred process which comprises the following steps: a) trioxane, methylal and optionally dioxolane are introduced as solution in a first reactor, b) the polymerization is started by addition of an initiator of the cationic polymerization at such pressures and temperatures in that the resulting polymer precipitates out of the reaction mixture, c) the reaction mixture containing the precipitated polymer is transferred from the first reactor to a second reactor, d) adding to the reaction mixture a base and optionally trioxane and / or dimethylacetamide containing a base dissolved therein such that the content of trioxane and optionally of dimethylacetamide in the second reactor is at least 10% by weight, based on the polymer, e) the reaction mixture in the second reactor is heated to a temperature such that the polymer dissolves, f) the reaction mixture is discharged from the second reactor, and g) the deactivated polymer freed from trioxane and optionally present dimethylacetamide.
- the invention therefore also relates to oxymethylene homopolymers optionally having up to 0.5% by weight of copolymerized oxyethylene units and / or up to 1% by weight of copolymerized branching agents in which at least 95% of all end groups, preferably at least 99%, are present. all end groups, and in particular at least 99.9% of all end groups are alkoxy radicals, wherein the
- Oxymethylene homopolymers having a decomposition rate, measured at 222 0 C, of less than 0.005 wt .-% / minute, preferably of less than 0.001 wt .-% / minute.
- the rate of decomposition is measured as described in US-A-3,161,616.
- the thermal decomposition of the polymer at 222 ° C. in an inert gas atmosphere is determined, which can be approximately represented as a first-order reaction.
- the decomposition rate k becomes the constant of the differential equation
- w means the weight of the polymer that is undecomposed after the time t has elapsed.
- Particularly preferred polymers have at least 99%, based on all end groups, in particular at least 99.9% alkoxy as end groups, preferably methoxy.
- Very particularly preferred oxymethylene polymers have a decomposition rate as measured at 222 0 C, of less than 5 * 10 "4 wt .-% / minute.
- Volume melt index MVR from 1 to 80 ml / 10 min, measured according to EN ISO 1133 at 190 0 C and at a load of 2.16 kg.
- the oxymethylene homopolymers and copolymers prepared according to the invention can be prepared in a manner known per se by molding processes, for example by blow molding,
- Injection molding or extrusion to be processed into moldings.
- the particularly preferred oxymethylene homopolymers are characterized by a high chemical and thermal stability and show excellent impact resistance.
- trioxane 100 parts by weight of trioxane were mixed with the proportions of methylal indicated in the table. 100 g of this mixture were placed in a tempered to 80 ° C, dried aluminum tube. The tube was sealed and annealed in a water bath at a temperature of 80 0 C over a period of 10 minutes. Thereafter, 0.1 ppm of trifluoromethanesulfonic acid (based on trioxane) as a 0.1 weight percent solution in diethyl glycol dimethyl ether was added via syringe. The polymerization solution was shaken vigorously until used the polymerization reaction. After solidification of the reaction mixture, the aluminum tube was stored for a further 30 minutes at the reaction temperature of 80 0 C. Subsequently, the sample was cooled, crushed and dissolved in dimethylacetamide containing 1,000 ppm of triethylamine. After evaporation of the solvent in vacuo, the MVR of the resulting POM
- Homopolymers determined. The measurement was carried out according to DIN ISO 1133 at 190 ° C with a weight of 2.16 kg.
- the polymer was boiled in methanol instead of dissolving in dimethylacetamide.
- Solvent leads to a significant molecular weight degradation of the polymer.
- the rate of decomposition of the polymer of Example 2 was determined at 222 ° C. in an inert gas atmosphere.
- the weight loss was 145 ppm / h.
Abstract
Description
Claims
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DE200510062326 DE102005062326A1 (de) | 2005-12-24 | 2005-12-24 | Verfahren zur Herstellung von Oxymethylen-Polymeren, ausgewählte Polymere und deren Verwendung |
PCT/EP2006/012028 WO2007073874A1 (de) | 2005-12-24 | 2006-12-14 | Verfahren zur herstellung von oxymethylen-polymeren, ausgewählte polymere und deren verwendung |
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EP1969024A1 true EP1969024A1 (de) | 2008-09-17 |
EP1969024B1 EP1969024B1 (de) | 2015-04-22 |
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EP20060840978 Not-in-force EP1969024B1 (de) | 2005-12-24 | 2006-12-14 | Verfahren zur herstellung von oxymethylen-polymeren |
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EP (1) | EP1969024B1 (de) |
JP (1) | JP5567779B2 (de) |
CN (2) | CN101346404A (de) |
DE (1) | DE102005062326A1 (de) |
WO (1) | WO2007073874A1 (de) |
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JP2009203347A (ja) * | 2008-02-28 | 2009-09-10 | Asahi Kasei Chemicals Corp | ポリアセタール樹脂の製造方法 |
JP5588598B2 (ja) * | 2008-03-18 | 2014-09-10 | 旭化成ケミカルズ株式会社 | ポリアセタール樹脂の製造方法 |
DE102008018966A1 (de) * | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Verfahren zur Herstellung von Oxymethylen-Polymeren und dafür geeignete Vorrichtung |
DE102008018968A1 (de) * | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Polyoxymethylen-Formmassen und Formkörper und deren Verwendung |
DE102008018967A1 (de) * | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Oxymethylenpolymere, Verfahren zu deren Herstellung und deren Verwendung |
DE102008018965A1 (de) | 2008-04-16 | 2009-10-22 | Ticona Gmbh | Oxymethylen-Copolymere und deren Verwendung sowie Verfahren zur Herstellung von Oxymethylen-Copolymeren |
US8840976B2 (en) | 2010-10-14 | 2014-09-23 | Ticona Llc | VOC or compressed gas containment device made from a polyoxymethylene polymer |
EP2505609B1 (de) | 2011-04-01 | 2015-01-21 | Ticona GmbH | Polyoxymethylen mit hoher schlagfestigkeit für extrusionsblasformung |
US8968858B2 (en) | 2011-12-30 | 2015-03-03 | Ticona Llc | Printable molded articles made from a polyoxymethylene polymer composition |
US9745467B2 (en) | 2012-12-27 | 2017-08-29 | Ticona, Llc | Impact modified polyoxymethylene composition and articles made therefrom that are stable when exposed to ultraviolet light |
KR20210008507A (ko) * | 2018-05-09 | 2021-01-22 | 바스프 에스이 | 착색된 폴리옥시메틸렌 공중합체의 제조 방법 |
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IT1051892B (it) * | 1975-12-23 | 1981-05-20 | Sir Soc Italiana Resine Spa | Procedimento per migliorare la stabilita degli omopolimeri acetalici eterificati |
IT1051890B (it) * | 1975-12-23 | 1981-05-20 | Sir Soc Italiana Resine Spa | Procedimento migliorato per la stabilizzazione di omopolimmeri acetalici eterificati e di copolimeri acetalici |
IT1076228B (it) * | 1977-01-17 | 1985-04-27 | Sir Soc Italiana Resine Spa | Procedimento atto a migliorare la stabilita' degli omopolimeri acetalici eterificati |
JPS54139697A (en) * | 1978-04-21 | 1979-10-30 | Asahi Chem Ind Co Ltd | Preparation of stabilized polyoxymethylene |
JPH0235772B2 (ja) * | 1981-08-25 | 1990-08-13 | Asahi Chemical Ind | Horiokishimechirenkyojugobutsunoshitsukatsukahoho |
JPS58167608A (ja) * | 1982-03-29 | 1983-10-03 | Asahi Chem Ind Co Ltd | 重合触媒失活法 |
JPS6063216A (ja) * | 1983-09-16 | 1985-04-11 | Polyplastics Co | 熱安定性,成形性の改良されたポリアセタ−ル重合体の製造法 |
JPS61209217A (ja) * | 1985-03-14 | 1986-09-17 | Japan Synthetic Rubber Co Ltd | オキシメチレン共重合体の製造方法 |
US4788258A (en) * | 1987-09-14 | 1988-11-29 | Hoechst Celanese Corporation | Low Tg non-crystalline acetal copolymers |
JP3168034B2 (ja) * | 1991-10-04 | 2001-05-21 | 旭化成株式会社 | ポリオキシメチレン製ギア |
JPH0598028A (ja) * | 1991-10-07 | 1993-04-20 | Asahi Chem Ind Co Ltd | ポリオキシメチレン製押出成形品 |
JP3017376B2 (ja) * | 1993-06-18 | 2000-03-06 | ポリプラスチックス株式会社 | 高重合度ポリオキシメチレン3元共重合体の製造方法 |
DE4327245A1 (de) * | 1993-08-13 | 1995-02-16 | Hoechst Ag | Verfahren zur Herstellung von Polyacetalen |
DE4423617A1 (de) * | 1994-07-06 | 1996-01-11 | Hoechst Ag | Verfahren zur Herstellung von Polyacetalen |
US6365655B1 (en) * | 1997-03-26 | 2002-04-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for stabilizing oxymethylene copolymer |
JP3208351B2 (ja) * | 1997-06-17 | 2001-09-10 | ポリプラスチックス株式会社 | ポリアセタール樹脂の製造方法 |
JP2000290336A (ja) * | 1999-04-02 | 2000-10-17 | Mitsubishi Gas Chem Co Inc | 重合反応の停止方法 |
JP4247586B2 (ja) * | 1999-04-02 | 2009-04-02 | 三菱瓦斯化学株式会社 | 重合反応の停止方法 |
JP2000290335A (ja) * | 1999-04-06 | 2000-10-17 | Mitsubishi Gas Chem Co Inc | 重合反応の停止方法 |
JP4997717B2 (ja) * | 2004-06-21 | 2012-08-08 | 三菱瓦斯化学株式会社 | 無色透明性ポリイミド複合フィルムおよびその製造方法 |
DE102004057867A1 (de) * | 2004-11-30 | 2006-06-01 | Basf Ag | Verfahren zur Herstellung von Polyoxymethylenen |
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- 2005-12-24 DE DE200510062326 patent/DE102005062326A1/de not_active Withdrawn
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- 2006-12-14 CN CNA2006800490339A patent/CN101346404A/zh active Pending
- 2006-12-14 JP JP2008546205A patent/JP5567779B2/ja not_active Expired - Fee Related
- 2006-12-14 EP EP20060840978 patent/EP1969024B1/de not_active Not-in-force
- 2006-12-14 CN CN201410060312.1A patent/CN103881041A/zh active Pending
- 2006-12-14 WO PCT/EP2006/012028 patent/WO2007073874A1/de active Application Filing
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JP5567779B2 (ja) | 2014-08-06 |
EP1969024B1 (de) | 2015-04-22 |
JP2009521537A (ja) | 2009-06-04 |
CN101346404A (zh) | 2009-01-14 |
DE102005062326A1 (de) | 2007-06-28 |
WO2007073874A1 (de) | 2007-07-05 |
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